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Journal of Colloid and Interface Science 284 (2005) 606613 www.elsevier.


Catalytic dehydration of ethanol using transition metal oxide catalysts

T. Zaki
Egyptian Petroleum Research Institute, Nasr City, Post Box 11727, Cairo, Egypt Received 3 September 2004; accepted 20 October 2004 Available online 13 December 2004

Abstract The aim of this work is to study catalytic ethanol dehydration using different prepared catalysts, which include Fe2 O3 , Mn2 O3 , and calcined physical mixtures of both ferric and manganese oxides with alumina and/or silica gel. The physicochemical properties of these catalysts were investigated via X-ray powder diffraction (XRD), acidity measurement, and nitrogen adsorptiondesorption at 196 C. The catalytic activities of such catalysts were tested through conversion of ethanol at 200500 C using a catalytic ow system operated under atmospheric pressure. The results obtained indicated that the dehydration reaction on the catalyst relies on surface acidity, whereas the ethylene production selectivity depends on the catalyst chemical constituents. 2004 Elsevier Inc. All rights reserved.
Keywords: Catalysis; Dehydration; Ethanol; Iron; Manganese

1. Introduction Ethylene is an essential material for the petrochemical industry. Catalytic dehydration of ethanol into ethylene was investigated using different transition metal catalysts such as titanium oxides [1,2], magnesium oxides [3,4], cobalt oxides [5,6], chromium oxide [7], silver salt of tungstophosphoric acid [8], Fe2 O3 /Al2 O3 [9], FeOx /Al2 O3 (prepared using iron and aluminum oxides recovered from steel-pickling chemical waste and aluminum dross tailings, respectively) [10], Fe2 O3 , CoO, and NiO/clay [11], iron ion-exchanged mordenite [12], and Na2 O-doped Mn2 O3 /Al2 O3 [13]. Also, ethanol dehydration was studied using aluminum and/or silicon oxide materials [1417]. In this work, the catalytic efciency of different prepared catalysts, Fe2 O3 , Mn2 O3 , and calcined physical mixtures of both ferric and manganese oxides with alumina and/or silica gel, toward the dehydration of ethanol into ethylene is investigated.

2. Experimental 2.1. Samples preparation The different prepared catalysts are included in Table 1. Cat1 is prepared from freshly precipitated ferric hydroxide (the precursor compound was hydrated ferric nitrate, Laboratory Rasayan, assay >98%), and then calcined at 500 C in a stream of puried air for 5 h. Cat2 is prepared using the precursor compound manganese nitrate (Laboratory Rasayan, assay >98%), and the calcination step was at temperature 700 C. Hybrid catalysts, Cat3Cat6, were obtained through the physical mixing of their components in different percentages as presented in Table 1 (neutral type alumina, Merck, and silica gel, Merck), and then calcined at temperature 700 C. 2.2. Structure and phase changes investigation 2.2.1. X-ray diffraction analysis The X-ray diffraction patterns of the studied materials were recorded in the 2 range of 4 70 in a Brukur B8 advance diffractometer with CuK1 radiation of wavelength 1.541 . The instrument was operated at 40 kV and the

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T. Zaki / Journal of Colloid and Interface Science 284 (2005) 606613


Table 1 Chemical composition of the different six catalysts Sample code Cat1 Cat2 Cat3 Cat4 Cat5 Cat6 Molar percentage Mn2 O3 0 100 50 45 45 31 Fe2 O3 100 0 50 45 45 53 Al2 O3 0 0 0 10 0 6 SiO2 0 0 0 0 10 10

spectra were recorded at a scanning rate of 8 /min. The information concerning the crystalline phases was obtained by comparing the characteristic d-spacing () and the relative intensity I /I0 with the data given in the ASTM cards. 2.2.2. Nitrogen adsorptiondesorption technique The specic surface area (SBET ), total pore volume (Vp ), and mean pore radius (rH ) of the different samples were measured using a Quantachrome NOVA-2000 automated gas sorption system. Prior to such measurements all samples were perfectly degassed at 150 C and evacuated at 104 Torr for 3 h. 2.2.3. Acidity Surface acidity measurements were carried out by irreversible adsorption of the organic bases pyridine (Py, pKa = 5.3) and piperidine (Pp, pKa = 11.1), using a technique similar to that applied by Mishra and Parida [18]. In each experiment, 0.1 g of the sample was weighed in an adsorption bottle and dried for 12 h at a temperature of 130 C. After cooling, 10 ml of the freshly prepared solution of the adsorbent in cyclohexane was pipetted into the adsorption bottle. The mixture was stirred for 2 h at ambient temperature. The amount adsorbed was determined using a UV spectrophotometer. Sorption experiments were developed at wavelength of maximum adsorption (max , nm) and in the concentration range of the adsorbate within which the Beer Lambert law was obeyed. These experiments were done with a standard deviation error of 0.1 (n = 3, where n is the number of experiment repetitions). The adsorption of the substrate from solution was found to obey a Langmuir adsorption isotherm. This method provides both the total concentration of acid sites and their relative strength by the use of organic bases with different pKa . 2.3. Dehydration reaction The dehydration of ethanol (EDWIC, assay > 99%) was carried out in a catalytic-ow-type system operated under atmospheric pressure. The reactant was dosed (liquid-hourspace-velocity equal to 2.85 h1 ) in a Pyrex glass reactor packed with 10 ml of the tested sample in the presence of a hydrogen stream (ow rate 75 ml/min). All experiments were carried out at reaction temperatures from 200 to 500 C.

Fig. 1. X-ray diffraction patterns for (a) Cat1, (b) Cat2, and (c) Cat3.

The reaction products were analyzed using a gas chromatograph manufactured by PerkinElmer, Model Sigma 3B, using a separation column 20 m in length packed with 20 wt% silicon oil supported on chromosorb-P 80100 mesh size.

3. Results and discussion 3.1. Structure and phase changes investigation 3.1.1. X-ray diffraction analysis The X-ray diffraction pattern of Cat1 (Fig. 1a) reveals the main reections of ferric oxide at d-distances 2.69, 2.51, and 1.69 (ASTM Card No. 89-0599). Fig. 1b represents the diffraction pattern of Cat2, which illustrates the reections of manganese II oxide at d-distances 3.84, 2.72, and 1.66 (ASTM Card No. 10-0069). The X-ray diffraction pattern for hybrid Cat3 (Fig. 1c) reveals the main reections of both oxides as well as reections at d-distances 2.69, 1.66, and 1.42 , which indicates the formation of the new phase FeMnO3 (ASTM Card No. 75-0894). Fig. 2a shows a slight increase in the relative intensities of ferric and manganese oxides as a result of their mixture with alumina species in hybrid Cat4. The absence of the peaks, which may be originated from silica or alumina species (Figs. 2a, 2b, and 2c), may be attributed to their amorphous nature.


T. Zaki / Journal of Colloid and Interface Science 284 (2005) 606613

Finally, the calculations of species average crystallite size of iron and manganese oxides according to their main reections at d-distances of 2.69, 2.72, and 1.66 successively indicate an increase in the values of ferric oxide crystallite size and a decrease for those related to manganese oxide in a followup of the physical mixing process (Cat36), as shown in Table 2.

Fig. 2. X-ray diffraction patterns for (a) Cat4, (b) Cat5, and (c) Cat6. Table 2 Calculated average crystallite size values of the different catalysts 2 32.95 33.20 d () 2.72 2.69 Average crystallite size (nm) Cat1 57.3 Cat2 149.3

3.1.2. Nitrogen adsorptiondesorption technique Nitrogen adsorptiondesorption isotherms at liquid nitrogen temperature (196 C) for the prepared catalysts were found to have reversible isotherms exhibiting close hysteresis loops of type H3 (slit-shaped pores or plate-like particles) according to the classication of IUPAC manual [20]. The values for surface area and pore radius of Fe2 O3 , Mn2 O3 , alumina, silica, and the different hybrid catalysts are presented in Table 3. The data revealed that the surface area of the hybrid catalysts 3 and 4 with respect to that of Cat1 (ferric oxide) were very small; on the other hand, an enlargement for the others (catalysts 5 and 6) was found. The decrement in surface area for Cat3 and 4 may be due to the mixture of iron oxide with low-surface-area manganese oxide. The increment in the surface area of hybrid catalysts 5 and 6 may be related to the high-surface-area contaminated silica (ABET , 404.2 m2 /g). The pore size distribution data for the parent and the prepared hybrid catalysts are represented in Fig. 3. Cat1 exists within a wide mesoporous range (pore radius ranged from 35 to 85 ), while for Cat2 the distribution is concentrated in a narrow range (pore radius ranged from 18 to 30 ). This may be veried from X-ray analyses, which indicate various diffraction lattices due to the great difference in the mean pore radii of such catalysts. Moreover, the variation in the pore size distribution of both Cat3 and Cat4, and consequently the creation of new pores, may be due to the intrusion of manganese oxide inside the very deep iron pore for Cat3 and correlated with the competition that occurred between manganese and aluminum oxides to intrude into the iron pore system (Cat4). On the other hand, Fig. 3e cleared the intrusion of the different existing pores; this may be related to the high value of the pore size distribution of the blended silica (Fig. 3h). The Vl t plots (Fig. 4) indicated that all catalysts were meso-

Cat3 92.7 115.6

Cat4 62.8 104.9

Cat5 75.4 95.5

Cat6 82.2 118.0

Table 3 Textural and surface acidity of samples Sample code Cat1 Cat2 Cat3 Cat4 Cat5 Cat6 Alumina Silica ABET (m2 /g) 40.34 19.46 24.89 27.79 41.68 58.00 85.27 404.20 At (m2 /g) 42.55 20.92 26.83 29.69 42.64 60.98 Vp (ml/g) 0.0349 0.0074 0.0105 0.0122 0.0419 0.0565 0.0637 0.3073 rH () 17.30 7.61 8.44 8.78 20.11 19.48 17.64 31.68 Surface acidity (mol/m2 ) Piperidine 17.28 8.22 15.55 16.62 12.52 9.95 Pyridine 1.93 0.72 0.88 1.04 1.10 1.10

Note. ABET is the BET surface area, rH is the value of the average pore radius, and Vp is the total pore volume.

T. Zaki / Journal of Colloid and Interface Science 284 (2005) 606613


Fig. 3. Pore size distribution patterns for (a) Cat1, (b) Cat2, (c) Cat3, (d) Cat4, (e) Cat5, (f) Cat6, (j) alumina, and (h) silica.

pores in nature. The calculated At obtained from such plots are given in Table 3, and the agreement between ABET and At indicates the correct choice of the reference t values selected on the basis of the value of CBET [21]. 3.1.3. Acidity The nature of acid sites may be dened by the presence of surface protons, leading to the Brnsted sites, or cationic centers arising due to unsaturation in coordination, which explain the Lewis acidity. Piperidine is a strong base that adsorbed on all types of acid centers and represents total acidity of the samples. On the other hand, pyridine is adsorbed only on the strong acid sites [22]. Surface acidity values of different catalysts in Table 3 illustrate the high total acidity of Cat1, Cat4, and Cat3 successively with respect to the rest of the catalysts according to the adsorbed piperidine.

3.2. Ethanol catalytic dehydration The experimental data for catalytic activities of the different prepared catalysts toward ethanol dehydration reaction are shown in Table 4 and illustrated in Figs. 57. It is clear from data in Table 4 that the total conversion increased continuously with increasing reaction temperature for all prepared catalysts. Ethylene and diethyl ether were rather dominant products, while acetaldehyde and ethane were rather less dominant products. The inuence of reaction temperature on the total dehydrated products in Fig. 5 revealed that the yield of products increased smoothly with the continuous increase in reaction temperature from 200 to 500 C, and the percentage of the total dehydrated products increased gradually from 19.2 to 71.2% for Cat1. Cat2 behaves in a similar catalytic manner with increased experiment temperature. However, the


T. Zaki / Journal of Colloid and Interface Science 284 (2005) 606613

Fig. 3. Continued. Table 4 Inuence of reaction temperature on total conversion percentage Reaction temperature ( C) 200 250 300 350 400 450 500 Total conversion (%) Cat1 42.55 59.61 62.22 82.18 87.74 96.17 96.96 Cat2 38.30 47.64 56.13 68.16 88.16 87.49 90.10 Cat3 31.50 42.30 46.30 76.00 87.58 91.81 94.30 Cat4 43.47 57.70 70.28 92.09 92.30 93.62 95.28 Cat5 55.48 81.48 95.46 98.48 98.92 99.37 99.65 Cat6 52.70 72.89 79.71 92.20 94.44 95.85 96.00

total dehydrated products that formed using this catalyst are less than those produced via Cat1, whereas the total dehydration percentage reached its maximum value of 55.1% at a temperature of 500 C. On the other hand, the optimum reaction temperature required for the dehydration reaction is shifted downward to 400 C using Cat3, which is an equimolar ironmanganese oxide catalyst. Also the value

of dehydration percentage at the optimum temperature increased up to 66.7%. The total dehydration percentage increases gradually from 20.5 to 59.7% by elevating the reaction temperature from 200 to 450 C by using Cat4 (ironmanganesealuminum oxides catalyst). With further increases in reaction temperature no noticeable increase in the dehydration percentage is detected.

T. Zaki / Journal of Colloid and Interface Science 284 (2005) 606613


Fig. 4. Vl t plots of the different catalysts.

Fig. 5. Effect of reaction temperature on the total dehydration of ethanol.

Fig. 6. Effect of reaction temperature on the selectivity towards ethylene production.

Upon using the fth catalyst (ironmanganesesilicon oxide catalyst), the experimental data showed high catalytic activity with continuous increase in the reaction temperatures with respect to the other catalysts, where the conversion values increased from 30.0 to 71.4%. On using Cat6, the dehydration reaction increases linearly from 27.5 to 66.7% by raising the temperature from 200 to 450 C, and reaches its maximum value of 68.7% at a temperature of 500 C. The previous results were conrmed strongly by the data from surface acidity measurements (Table 3), where the most active catalysts (Cat5, Cat6, and Cat1) are those that

have the highest values for pyridine adsorption (strong acid sites) and the less active catalyst has the least acidic sites (Cat2). These results agree well with what is well known, that the alcohol dehydration reactions are frequently employed to probe the acidic properties of solid surfaces [3,13]. The dehydrated products of ethanol are ethylene via intramolecular reaction and diethyl ether via intermolecular dehydration reaction. The selectivity values of the different catalysts toward the production of the former product are diagrammed in Fig. 6. The iron catalyst (Cat1) showed a gradual increase in the selectivity values from 3.8 to 65.4%


T. Zaki / Journal of Colloid and Interface Science 284 (2005) 606613

this shielding effect increases with the size of the water cluster. At lower reaction temperatures, the shielding effect is also enhanced, while at higher temperatures, this cluster is much smaller and the number of bridging protons increases, which directs ethylene formation. The selectivity values of the tested catalysts toward the production of the intermolecular dehydration product, diethyl ether are illustrated in Fig. 7, where the catalytic behaviors of selectivity of the different catalysts are approximately mirror images of those related to ethylene formation (Fig. 6); i.e., the dehydration of ethanol to ethylene is increased with increased reaction temperature, while the diethyl ether formation is decreased. This may be attributed to the requirement of intermolecular dehydration of ethanol (needs 2 mol) to form diethyl ether at a lower energy than the intramolecular dehydration of ethanol to form ethylene.

4. Conclusion In summarizing the results shown above, the following conclusions can be deduced: There is a similarity in the inuence of reaction temperature on ethanol conversion when the different prepared catalysts are used. The total dehydration results are related strongly to the data obtained from surface acidity measurements, where the most dehydrated catalysts are those have the highest acidity measurements. From the ethylene production selectivity data, it can be said that catalysts composed of ironmanganese oxides and of ironmanganesesilica oxides possessed the highest selectivity; this may be in agreement with the role iron species, whereas the reducibility of ironactive species plays an important role in the oxidation processes [19].

Fig. 7. Effect of reaction temperature on the selectivity towards diethyl ether production.

with reaction temperature increasing to 500 C; meanwhile the manganese catalyst (Cat2) appears to have the lowest selectivity toward ethylene formation. The differentiation in the selectivity of both catalysts may be explained according to the catalysts surface acidity measurements (Table 3), whereas with decreasing surface acidity, the strength of adsorption of the ethanol on the acid sites diminished, and so the C2 H5 O bond become stronger, which leads to a preferred intermolecular reaction and decreasing rate of ethylene formation [4]. Cat3 (ironmanganese oxide catalyst) and Cat5 (ironmanganesesilica oxide catalyst) have the same selectivity; in addition, their maximum selectivity is achieved at a lower temperature of 400 C, as compared with that on Cat1 (Fig. 6). From the previous data it can be said that both Cat3, and Cat5 possessed the highest selectivity. This may be in agreement with the role of iron species, as the reducibility of iron-active species plays a key role in the oxidation processes [19]. Also, the relatively high dehydration activities for catalysts containing iron oxide at the lower reaction temperatures is in good agreement with results performed by Riad et al. [11], who explained it based on the water molecules produced during the dehydration of ethanol, which facilitate the hydration of the Brnsted acid sites, forming dimeric (H2 O+ ) or tetrameric water (H5 O+ ) ac2 cording to Krossner and Somers proposal [23]. The forming of dimeric water is the preferred state of larger water clusters within higher surface coverage (4-atoms). These clusters have also a unique effect on the carbonium transition state, which shields the carbonium ion from nucleophilic attack by another adsorbed ethanol molecule, thus allowing the competing -elimination reaction to prevail. The efciency of

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